Liquid anhydrous stannous soap compositions



United States Patent 3,262,889 LIQUID ANHYDROUS STANNOUS SOAP COMPOSITIONS Leonard M. Edwards, Cranford, and Otto E. Loeffier, Rahway, N.J., assignors, by mesne assignments, to MT. Chemicals Inc., New York, N.Y., a corporation of Delaware No Drawing. Filed Feb. 27, 1962, Ser. No. 176,112 20 Claims. (Cl. 252-431) This invention relates to novel metal soap compositions and to a method for making the same. More specifically, it relates to metal soap compositions with novel physical characteristics and a method for preparing them.

As is well known to those skilled in the art, soaps of heavy metals, typified by tin, may be made by a number of processes. Those processes Which have been most widely used are the fusion process, and the double decomposition process.

The fusion or neutralization process involves the reaction of a compound of a metal, typically the oxide or hydroxide, with an acid to give the desired soap. Typical of such a reaction would be the formation of stannous oleate:

The double decomposition process involves the reaction of a salt of the desired metal ion with a soap of a different metal ion:

H2O 2Ci Ha3COONa SnClz (C17HaaCOO)2SI1 ZNaCl Whatever process is used, it will be highly desirable to eliminate substantially all of the water contained in the metal soap product. This water may be present as a reaction product, as in reaction 1), or as an impurity contained in the reactants. The necessity for removing substantially all the water present in the product metal soap may be explained by a consideration of reaction 1), a reversible reaction. According to this reaction, Water may react with the product metal soap to give the metal oxide or hydroxide and the corresponding acid of the soap anion. The reduction of the metal soap content of the product will be found to lower the effectiveness of the soap composition in the use for which it was made.

For these reasons, it is highly desirable to produce metal soaps which are substantially anhydrous, that is soaps which contain less than about 0.5 water. These anhydrous metal soaps, typically about 99.5% anhydrous, are characterized by certain physical characteristics. Most of them are Waxy solids. Others may be heavy pastes or viscous, oily, relatively immobile syrups. Metal soaps characterized by these physical forms may be difficult to handle, measure, blend, etc. In order to overcome these difficulties, it has been common to add a diluent to the metal soap product. Such diluents, e.g. mineral spirits, have necessarily been employed at high levels of concentration, thereby yielding a composition with a considerably reduced percentage of active metal soap and, consequently, reduced effectiveness in the desired use. Accordingly, it has not heretofore been possible to prepare liquid metal soap compositions which are both easily handled and contain a high percentage of active metal soap.

It is an object of this invention to provide a method for preparing liquid soap compositions. It is a further object of this invention to provide novel liquid soap compositions containing a high percentage of active metal soap.

In accordance with certain of its aspects, the process of this invention may comprise adding to a substantially anhydrous soap selected from the group consisting of stannous oleate, stannous linoleate, stannous linolenate, and mixtures thereof, a liquifying amount of a compound RI R(OH).. N RII b wherein R is a hydrocarbon radical selected from the group consisting of alkyl, aryl, aralkyl, alkenyl, cycloalkyl and cycloalkenyl radicals and polyvalent radicals derived therefrom; a and b are small integers and a+b is at least one; and R and R" are selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, .alkenyl, cycloalkyl, cycloalkenyl and hydrogen.

The metal soaps which may be liquified by the process of this invention may commonly be substantially anhydrous metal soaps having anions which are derived from high molecular weight ethylenically unsaturated hydrocarbon acids. Typically, these metal soaps may be made by the reaction of metal oxide with acid according to the fusion process, or by the reaction of a salt of the acid with a salt of the metal according to the double decomposition process. Although the metal soap prepared in this manner may be commonly designated as e.g. stannous oleate, it may contain a substantial proportion of compositions similar to this material.

The illustrative soaps which may be liquified by the process of this invention may be those wherein the anion may be derived from an ethylenically unsaturated hydrocarbon acid such as oleic acid, linoleic caid, linolenic acid, etc. Typical of the preferred soaps which may be liquefied may be noted those commonly designated as stannous oleate, stannous linoleate, and stannous linolenate.

It is a particular feature of the liquifying technique of this invention that it may be particularly effective when used in connection with soaps which are substantially anhydrous. These substantially anhydrous soaps may be characterized by the presence of Water in amount sufficiently small to minimize or substantially eliminate any appreciable degree of hydrolysis under normal handling conditions. Typically a soap may be considered substantially anhydrous when it contains less than about 0.5% by weight of water, and such soaps commonly may be either waxy solids, or heavy pastes, or viscous, oily, relatively immobile syrups.

The liquifying compounds or liquifiers contemplated in the practice of this invention are compounds of the formula wherein R may be' an alkyl radical including branched alkyls, an aryl radical, an aralkyl radical, an alkenyl radical, a cycl-oalkyl radical, a cycloalkenyl radical or a polyvalent radical derived therefrom, etc. and a and b are small integers whose sum is at least one. The substituent R may be .an alkyl radical; typical radicals may include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, sec-butyl, t-butyhamyl, hexyl heptayl, octyl nonyl decyl, etc. ethylene (-CH CH propylene (-C H butylene (C H trimethylene, etc. propane tri-yl (i.e. a trivalent radical derived from propane e.g. 1,2,3- propane tri-yl) etc. Typical aryl radicals may include phenyl, naphthyl, etc. Typical aralkyl radicals may include benzyl, cinnamyl, w-phenyl butyl, etc. Typical alkenyl radicals may include allyl, butenyl, pentenyl, etc. Typical cycloalkyl radicals may include cyclohexyl, cyclopentyl, etc. Typical cycloalkenyl radicals may include cyclohexenyl, etc.

In certain aspects of this invention, b will be and a will be a small integer, say 1-6, and the compound will be R(OH),,, i.e. an alcohol, a phenol, a glycol, a polyol, etc. For example, R(OH),, may be ethanol, isopropanol, n-butanol, n-octanol, t-butanol, n-propanol, allyl alcohol, benzyl alcohol, cyclohexanol, cyclohexenol, phenol, resorcinol, hydroquinone, ethylene glycol, propylene glycol, glycerine, sorbitol, mannitol, lauryl alcohol, stearyl alcohol, etc. Preferably, when b is 0, R will be an alkyl radical and a will be 1, 2, or 3. Preferably, the liquifier R(OH) will be an aliphatic alcohol, e.g. ethanol, butanol; an aliphatic glycol, e.g. ethylene glycol, propylene glycol; or an aliphatic triol, e.g. glycerine.

In accordance with certain other aspects of this invention a may be 0 and b will be a small integer, say 1-6,

and the compound R) R" b i.e. an amine including primary, secondary, and tertiary amines, a diamine, a polyamine, etc. The substituent radicals R and R may typically be hydrogen, alkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkenyl, and cycloalkyl. R' may be same as or dilferent from R", and either may be the same as or different from R. R and R" may typically be alkyl, e.g. methyl, ethyl, propyl, i-propyl, butyl, i-butyl, sec-butyl, t-butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, etc. R and R" may typically be aryl, e.g. phenyl, naphthyl, etc. R and R may typically be aralkyl, e.g. benzyl, cinnamyl, w-phenyl butyl, etc. R and R" may typically be alkenyl, e.g. allyl, buten-yl, penten-yl, etc.', or cycloalkenyl e.g cyclohexenyl, etc.; or cylcoalkyl e.g. cyclohexyl, cyclopentyl, etc.; or alkaryl, e.g. tolyl, xylyl, etc.

will be It will be understood that the R, R and R substituents may be polyvalent, e.g. divalent and may, by joining with each other or with nitrogen atoms form cyclic structures, e.g. N-ethyl morpholine, triethylene diamine, pyrrole, pyrroline, etc.

When both R and R radicals are hydrogen, the compound RI RN will be a primary amine, e.g. ethylamine, aniline, n-dodecyl amine, isopropylamine, allylamine, ethylene diamine, n-butylamine, amylamine, cyclohexylamine, cyclohexenylamine, etc.

When R is hydrogen, and R is a hydrocarbon radical,

'will be a secondary amine, e.g. diethylamine, propylethylamine, N-methylaniline, diphenylamine, N,N'-dimethylethylenediamine, diisopropyl-amine, di-n-butylamine, etc.

When both of the R and R" are hydrocarbon radicals,

will be a tertiary amine, e.g. triethylamine, N,N-dimethyl aniline tri-n-butylamine, triisopropylamine, diethylpropylamine, ethylpropylbutylamine, etc.

Preferably when a is 0, R will be an alkyl radical, R and R will be hydrogen or alkyl radicals, and

will be a primary, secondary, or tertiary aliphatic amine.

When neither a nor b is 0,

Liquifying amounts of the compound morn. N

may vary for each of the particular compounds. Typically, it may be 0.5%3.0% preferably 0.5%2.0% by weight of the metal soap. Lesser amounts, down to e.g. 0.1%, may be employed but liquification may not thereby be attained as satisfactorily. Increased amounts of liquifiers may be employed if desired.

The liquifying compound may be incorporated into the metal soap composition by any procedure which will insure complete physical mixing, so that a homogeneous mixture is formed. It may be found that the liquifying compound may be added to the metal soap while it is in the solid state and that the soap will immediately begin to liquify, so that a homogeneous liquid composition may be obtained with relatively low-shear agitation. Shaking or tumbling may also be employed to facilitate the dispersion of the liquifier throughout the metal soap. When it is desired to obtain a liquid metal soap composition in a shorter perod of time, high speed or high-shear agitation may be employed, or the solid metal soap may be heated until it becomes liquid, commonly to 35-50" C. and the liquifying compound may then be rapidly dispersed therein. It will be found that the metal soap will then remain in a liquid state when cooled to room temperature; meal soaps so liquified may remain liquid for an idenfinitely long period of time. It is an outstanding feature of this invention that the liquifying compound may be added to and dispersed in the reaction mixture employed in the preparation of the metal soap. When this embodiment is practiced, the substantially anhydrous metal soap product may be obtained as a liquid, and the problems of handling and blending which are associated with solid metal soaps will thereby be completely avoided.

Thus the novel liquid metal soap compositions of this invention may consist essentially of a substantially anhydrous metal soap selected from the group consisting of stannous oleate, stannous linoleate, stannous linolenate and mixtures thereof; a liquifying amount of a compound Mott)a N wherein R is a hydrocarbon radical selected from the group consisting of the alkyl, aryl, aralkyl, alkenyl, cycloalkyl, and cycloalkenyl radicals; a and b are small integers and a-l-b is at least one; and R' and R are selected from the group consisting of alkyl, aryl alkaryl, aralkyl, cycloalkyl, cycloalkenyl, alkenyl, and hydrogen.

Illustrative liquid metal soap compositions prepared in accordance-with this invention may include:

a. Stannous oleate containing 2% ethylene glycol;

b. Stannous oleate containing 2% glycerine;

c. Stannous oleate containing 1% ethylene diamine;

d. Stannous linoleate containing 1% ethylene glycol;

e. Stannous linolenate containing 2% ethanol.

Practice of this invention may be further observed from inspection of the following examples.

In Examples 1-12, the noted liquifier was added to substantially anhydrous stannous oleate of high purity, having an analysis of 16.74% Sn+ and 17.88% total tin, and a water content of less than 0.5%. The liquifier and the metal soap were thoroughly mixed by hand. The liquefaction temperature of each mixture was then determined by cooling the mass until it became solid and slowly raising its temperature until it was completely liquid, i.e. free of solid material. The latter temperature was recorded as the liquefaction temperature. A liquefaction temperature below room temperature i.e. about C. may be satisfactory.

An inspection of the data of Examples 1-l2 reveals the unexpected ability of the compounds RI N to liquify substantially anhydrous metal soaps. It may be seen that even very small concentrations of the liquifying compound are effective in preventing solidification of the metal soap even at temperatures considerably lower than would commonly be found in areas where the metal soaps are employed. Ethylene glycol is especially effective as the liquifying agent. In fact, when ethylene glycol is used, it may be possible to prevent undesirable solidification of the metal soaps at temperatures below the freezing point of water.

In Examples 13-16 the procedure of Examples 1-12 was followed except that the sample of stannous oleate metal soap employed had an analysis of 16.4% Sn+ and 17.14% total tin.

Lique faction Example Liquifier Percent Temperature,

Liquifier 0.

None 0 45 Ethylene dia 1 9 Ethylene glycol 2 8 Liquifier Percent Physical State Liquifier Solid. Completely liq.

Triethylenediamine N-ethyl morpholine- When substantially anhydrous stannous linoleate or stannous linolenate is substituted for the stannous oleate of Examples 1732, the same results may be observed. Similar results may be obtained by using as the liquifier piperidine, ethyl amine, cyclohexanol, and cyclohexylamine.

The novel liquid soap compositions of this invention may be especially useful in areas wherein small quantities of metal soap must be measured and handled. Typical of such an area is the use of the metal soap as a catalyst, e.g. in the formation of polyurethane foams. Similarly, they may be used in other areas wherein prior art soap compositions have been employed.

Although this invention has been illustrated by reference to certain specific examples, many modifications thereof will be apparent to one skilled in the art which fall within the scope of the invention.

We claim:

1. The process for liquifying substantially anhydrous metal soaps which comprises adding to parts by weight of a soap selected from the group consisting of stannous oleate, stannous linolea-te, stannous linolenate, and mixtures thereof from 0.13.0 parts by weight of a compound Ru b wherein R is a hydrocarbon radical selected from the group consisting of alkyl, cycloalkyl, aryl, ar-alkyl, alkenyl, cycloalkenyl radicals and polyvalent radicals derived therefrom; a and b are integers from 0 to 6 and a-i-b is at least one; and R and R" are selected from the group consisting of alkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkenyl, cycloalkyl and hydrogen radicals.

2. The process for liquifying substantially anhydrous metal soaps as claimed in claim 1 wherein b is 0 and the compound is R(OH),,.

3. The process for liquifying substantially anhydrous metal soaps as claimed in claim 1 wherein a is 0 and the compound is is present in the amount of at least 0.5 part 100 parts by weight of metal soap.

5. The process for liquifying substantially anhydrous metal soaps as claimed in claim 1 wherein the metal soap is stannous oleate.

by weight per 6. The process for liquifying substantially anhydrous metal soaps as claimed in claim 1 wherein M011)n N RI! h is ethylene glycol.

7. The process for liquifying substantially anhydrous metal soaps as claimed in claim 1 wherein 8. The process for liquifying substantially anhydrous metal soaps as claimed in claim 1 wherein the compound R) RI! b is present in the amount of about 0.5-3.0 parts by weight per 100 parts by weight of metal soap.

9. The process for liquifying substantially anhydrous stannous oleate which comprises adding to 100 parts by weight of said stannous oleate about 0.5-3.0 parts by weight of a compound mom, N

wherein R is a hydrocarbon radical selected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, alkenyl, cycloalkenyl radicals and polyvalent radicals derived therefrom; a and b are integers from to 6 and (1+!) is at least one; and R and R" are selected from the group consisting of alkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkenyl, cycloalkyl and hydrogen radicals.

10. A novel liquid metal soap composition consisting essentially of substantially anhydrous metal soap selected from the group consisting of stannous oleate, stannous linoleate, stannous linolenate, and mixtures thereof; and from 0.13.0 parts by weight per 100 parts by weight of said metal soap of a compound RI Rll b wherein R is a hydrocarbon radical selected from the group consisting of the alkyl, aryl, aralkyl, alkenyl, cycloalkyl, and cycloalkenyl radicals and polyvalent radicals derived therefrom; a and b are integers from O to 6 and a+b is at least one; and R and R" are selected from the group consisting of alkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkenyl, cycloalkyl and hydrogen radicals.

11. A novel liquid metal soap composition as claimed in claim 10 wherein b is 0.

12. A novel liquid metal soap composition as claimed in claim 10 wherein a is 0.

13. A novel liquid metal soap composition as claimed in claim 10 wherein the compound is present in the amount of at least 0.5 part by weight per parts by weight of metal soap.

14. A novel liquid metal soap composition as claimed in claim 10 wherein the metal soap is stannous oleate.

15. A novel liquid metal soap composition as claimed in claim 10 wherein a) R b is ethylene glycol.

16. A novel liquid metal soap composition as claimed in claim 10 wherein R) R b is glycerine.

17. A novel liquid metal soap composition as claimed in claim 10 wherein the compound R) R b is present in the amount of about 0.53 parts by weight per 100 parts by weight of metal soap.

18. A novel liquid metal soap composition consisting essentially of 100 parts by weight of substantially anhydrous stannous oleate and about 0.5-2.0 parts by weight of a compound R(OH)L\ N\ R s wherein R is a hydrocarbon radical selected from the group consisting of the alkyl, aryl, aralkyl, alkenyl, cycloalkyl, and cycloalkenyl radicals and polyvalent radicals derived therefrom; a and b are integers from 0 to 6 and a+b is at least one; and R and R" are selected from the group consisting of alkyl, aryl, aralkyl, alkenyl, alkaryl, cycloalkenyl, cycloalkyl and hydrogen radicals.

19. A novel liquid metal soap composition consisting essentially of 100 parts of stannous oleate and about O.5- 2.0 parts of ethylene glycol.

20. A novel liquid metal soap composition consisting essentially of 100 parts of stannous oleate and about 0.5- 2.0 parts of glycerine.

References Cited by the Examiner UNITED STATES PATENTS 3/1887 Gieberman 2604l4 6/1964 Piechota et 'al. 252-431 OTHER REFERENCES Guthrie et al., Chemical Abstracts, vol. 39, 1945, col.

P. D. FREEDMAN, I. G. LEVITT,

Assistant Examiners. 

1. THE PROCESS FOR LIQUIFYING SUBSTANTIALLY ANHYDROUS METAL SOAPS WHICH COMPRISES ADDING TO 100 PARTS BY WEIGHT OF A SOAP SELECTED FROM THE GROUP CONSISTING OF STANNOUS OLEATE, STANNOUS LINOLEATE, STANNOUS LINOLENATE, AND MIXTURES THEREOF FROM 0.1-3.0 PARTS BY WEIGHT OF A COMPOUND
 10. A NOVEL LIQUID METAL SOAP COMPOSITION CONSISTING ESSENTIALLY OF SUBSTANTIALLY ANHYDROUS METAL SOAP SELECTED FROM THE GROUP CONSISTINGG OF STANNOUS OLEATE, STANNOUS LINOLEATE, STANNOUS LINOLENATE, AND MIXTURES THEREOF; AND FROM 0.1-3.0 PARTS BY WEIGHT PER 100 PARTS BY WEIGHT OF SAID METAL SOAP OF A COMPOUND 